Copper formazan reactive dyes having halotriazine ring

ABSTRACT

Novel copper formazan reactive dyes which contain one or two chromophoric radicals derived from a copper formazan of the formula ##STR1## where R 1  is hydrogen, hydroxysulfonyl, C 1  -C 4  -alkoxy or chlorine, R 2  is hydrogen or hydroxysulfonyl and one of the two radicals R 3  and R 4  is hydrogen and the other is hydroxysulfonyl or, if at least one of the two radicals R 1  and R 2  is hydroxysulfonyl, R 3  and R 4  can each at the same time also be hydrogen, and two or three halotriazine radicals as reactive system, and salts thereof, are useful for dyeing or printing hydroxyl- or nitrogen-containing organic substrates.

The present invention relates to novel copper formazan reactive dyes ofthe formula I ##STR2## in the form of the free acid or in the form oftheir salts, wherein n is 0 or 1,

X¹ and X³ are identical or different, each being independently of theother chlorine or fluorine,

X² is chlorine, and

A is a radical of the formula IIa ##STR3## where R¹ is hydrogen,hydroxysulfonyl, C₁ -C₄ -alkoxy or chlorine,

R² is hydrogen or hydroxysulfonyl and

one of the two radicals R³ and R⁴ is hydrogen and the other ishydroxysulfonyl, or if at least one of the two radicals R¹ and R² ishydroxysulfonyl, R³ and R⁴ can each at the same time also be hydrogen,or a radical of the formula IIb ##STR4## where R¹ and R² are each asdefined above,

Z¹ and Z² are identical or different, each being independently of theother a radical of the formula III ##STR5## where R⁵ and R⁶ areidentical or different, each being independently of the other hydrogenor unsubstituted or cyano- or hydroxyl-substituted C₁ -C₄ -alkyl and

Y is hydroxyl or the radical NR⁷ R⁸, where R⁷ and R⁸ are identical ordifferent, each being independently of the other hydrogen orunsubstituted or cyano-, hydroxyl- or hydroxysulfonyl-substituted C₁ -C₄-alkyl, or the radicals R⁷ and R⁸ together with the nitrogen atomjoining them are a 5- or 6-membered heterocycle which may containfurther hetero atoms, and

B is chlorine, the radical NR⁹ R¹⁰, where R⁹ and R¹⁰ are identical ordifferent, each being independently of the other hydrogen orunsubstituted or cyano-, hydroxyl- or hydroxysulfonyl-substituted C₁ -C₄-alkyl, or one of the two radicals R⁹ and R¹⁰ may also be phenyl whichmay be substituted by hydroxysulfonyl, sulfamoyl, C₁ -C₄ -alkyl,halogen, cyano or C₁ -C₄ -alkoxy, or the radicals R⁹ and R¹⁰ togetherwith the nitrogen atom joining them are a 5- or 6-membered heterocyclewhich may contain further hetero atoms, or is the abovementioned radicalA,

with the proviso that a) R⁵ and R⁶ are not both hydrogen, b) when n is 0and B is A, at least one of the pairs A/B and X¹ /X² is different, c)when n is 1, B is A, and d) X² may also be fluorine when B is notchlorine.

DE-A-3,434,818 discloses copper formazan reactive dyes with amonochlorotriazine radical as reactive system. However, it has beenfound that the dyes described therein have inadequate applicationproperties, for example insufficient insolubility in the dyebath, lowcolor strength and inadequate color buildup if used in dyeing processesfor medium or deep shades.

Furthermore, earlier applications EP-A-315,046 and EP-A-315,047 describecopper formazan reactive dyes which are structurally similar to theabovementioned dyes of the formula I.

It is an object of the present invention to provide novel reactive dyesbased on copper formazans, which should have advantageous applicationproperties.

We have found that this object is achieved by the above-defined copperformazan reactive dyes of the formula I.

If in the formula I B is A, then, unless otherwise stated, the tworadicals A which appear in the formula may be identical or different.

R¹ is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy or sec-butoxy.

R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are each for example methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 1- or 2-cyanoprop-2-yl, 2- or 4-cyanobutyl, 2-hydroxyethyl,2- or 3-hydroxypropyl or 2- or 4-hydroxybutyl.

R⁷, R⁸, R⁹ and R¹⁰ are each further for example 2-hydroxysulfonylethyl,2- or 3-hydroxysulfonylpropyl or 2- or 4-hydroxysulfonylbutyl.

Y and B are each for example amino, mono- or dimethylamino, mono- ordiethylamino, mono- or dipropylamino, mono- or diisopropylamino, mono-or dibutylamino, N-methyl-N-ethylamino, mono- or bis(2-cyanoethyl)amino, mono- or bis(2-hydroxyethyl)amino, N-ethyl-N-(2-cyanoethyl)amino,N-ethyl-N-(2-hydroxyethyl)amino, 2-hydroxysulfonylethylamino orN-ethyl-N-(2-hydroxysulfonylethyl)amino.

Y is further for example pyrrolidino, piperidino, morpholino, piperazinoor N-(C₁ -C₄ -alkyl)piperazino such as N-methyl- or N-ethylpiperazino.

B is further for example phenylamino, N-methyl-N-phenylamino,N-ethyl-N-phenylamino, (2-, 3- or 4-hydroxysulfonylphenyl)amino, (2,4-or 2,5-dihydroxysulfonylphenyl)amino, (2- or3-methyl-4-hydroxysulfonylphenyl)amino,(2,5-dimethyl-4-hydroxysulfonylphenyl)amino,(5-chloro-2-hydroxysulfonylphenyl)amino,(4-methoxy-2-hydroxysulfonylphenyl)amino,(2-methoxy-4-hydroxysulfonylphenyl)amino,(2-chloro-5-hydroxysulfonylphenyl)amino,(2-methyl-5-hydroxysulfonylphenyl)amino,(2-ethyl-5-hydroxysulfonylphenyl)amino,(4-methoxy-3-hydroxysulfonylphenyl)amino,(4-chloro-3-hydroxysulfonylphenyl)amino,(4-methyl-3-hydroxysulfonylphenyl)amino,(2-chloro-3-methyl-5-hydroxysulfonylphenyl)amino,(2-chloro-4-methyl-5-hydroxysulfonylphenyl)amino,3-sulfamoylphenylamino, 3-(N-methylsulfamoyl)phenylamino,3-(N-ethylsulfamoyl)phenylamino, 3-(N,N-dimethylsulfamoyl)phenylamino,3-(N,N-diethylsulfamoyl)phenylamino,3-[N-(2-hydroxyethyl)sulfamoyl]phenylamino,3-[N,N-bis(2-hydroxyethyl)sulfamoyl]phenylamino,3-morpholinosulfonylphenylamino,[3-N-(2-hydroxysulfonylethyl)sulfamoylphenyl]amino,4-chloro-3-sulfamoylphenylamino,4-chloro-3-(N-methylsulfamoyl)phenylamino,4-chloro-3-(N-ethylsulfamoyl)phenylamino,4-chloro-3-(N,N-dimethylsulfamoyl)phenylamino,4-chloro-3-(N,N-diethylsulfamoyl)phenylamino,4-chloro-3-[N-(2-hydroxyethyl)-sulfamoyl]phenylamino,4-chloro-3-[N,N-bis(2-hydroxyethyl)sulfamoyl]phenylamino,4-chloro-3-morpholinosulfonylphenylamino,4-chloro-3-[N-(2-hydroxysulfonylethyl)sulfamoyl]phenylamino,4-methyl-3-sulfamoylphenylamino,4-methyl-3-(N-methylsulfamoyl)phenylamino,4-methyl-3-(N-ethylsulfamoyl)phenylamino,4-methyl-3-(N,N-dimethylsulfamoyl)phenylamino,4-methyl-3-(N,N-diethylsulfamoyl)-phenylamino,4-methyl-3-[N-(2-hydroxyethyl)sulfamoyl]phenylamino,4-methyl-3-[N,N-bis(2-hydroxyethyl)-sulfamoyl]phenylamino,4-methyl-3-morpholinosulfonylphenylamino or4-methyl-3-[N-(2-hydroxysulfonylethyl)sulfamoyl]phenylamino.

Suitable salts of the copper formazan reactive dyes of the formula I aremetal and ammonium salts. Metal salts are in particular the lithium,sodium and potassium salts. Ammonium salts for the purposes of thepresent invention are those salts which have either unsubstituted orsubstituted ammonium cations. Substituted ammonium cations are forexample monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- orbenzyltrialkyl-ammonium cations and those cations which are derived fromnitrogen-containing 5- or 6-membered saturated heterocycles, such aspyrrolidinium, piperidinium, morpholinium, piperazinium orN-alkyl-piperazinium cations or N-monoalkyl- or N,N-dialkyl-substitutedproducts thereof. Alkyl in this context is in general to be understoodas meaning straight-chain or branched C₁ -C₂₀ -alkyl which may besubstituted by hydroxyl and/or interrupted by oxygen.

Preference is given to copper formazan reactive dyes of the formula Iwhere Z¹ and Z² are each a radical of the formula IIIa ##STR6## where R⁵and R⁶ are each independently of the other, hydrogen, methyl or ethyl.

Particular preference is given to copper formazan reactive dyes of theformula I where Z¹ and Z² are each a radical of the formula IIIb##STR7## where R⁶ is methyl or ethyl.

Very particular preference is given to copper formazan reactive dyes ofthe formula Ia ##STR8## where R⁶ is methyl or ethyl and each A is asdefined above and different from the other A.

Very particular preference is further given to copper formazan reactivedyes of the formula Ib ##STR9## where R⁶ is methyl or ethyl, one of X¹and X² is chlorine and the other is fluorine, and each A, which may beidentical to or different from the other A, is independently of theother as defined above.

Very particular preference is further given to copper formazan reactivedyes of the formula Ic ##STR10## where Z¹ is a radical of the formulaIIIb ##STR11## where R⁶ is methyl or ethyl, X¹ and X² are eachindependently of the other chlorine or fluorine, and NR⁹ R¹⁰ is asdefined above.

Very particular preference is further given to copper formazan reactivedyes of the formula Id ##STR12## where A is as defined above, X¹ ischlorine or fluorine and Z¹ is a radical of the formula IIIb ##STR13##where R⁶ is methyl or ethyl.

Very particular preference is further given to copper formazan reactivedyes of the formula Ie ##STR14## where each A, which may be identical toor different from the other A, is independently of the other as definedabove, X¹, X² and X³ are each independently of the others chlorine orfluorine, and Z¹ and Z² are each independently of the other a radical ofthe formula IIIb ##STR15## where R⁶ is methyl or ethyl.

The novel copper formazan reactive dyes of the formula I can be preparedin a conventional manner. For example, dyes of the formula Ia areobtained by reacting cyanuric chloride with a copper formazan dye of theformula IV ##STR16## where R¹, R², R³ and R⁴ are each as defined above,to form a dichlorotriazine dye of the formula V ##STR17## where R¹, R²,R³ and R⁴ are each as defined above, which is then further reacted witha diamine of the formula VI ##STR18## where R⁵, R⁶ and Y are each asdefined above, to form a dye of the formula VII ##STR19## where R¹, R²,R³, R⁴, R⁵, and R⁶ and Y are each as defined above.

Reaction of the dye of the formula VII with a dichlorotriazine dye ofthe formula V other than the dye V already incorporated in dye VII givesthe dye of the formula Ia according to the present invention.

Dyes of the formula Ib are obtained for example by reacting cyanuricfluoride with a copper formazan dye of the formula IV to form thedifluorotriazine dye of the formula VIII ##STR20## where R¹, R², R³ andR⁴ are each as defined above, which is then further reacted with a dyeof the formula VII to form the dye of the formula Ib according to thepresent invention.

It is also possible to prepare dyes of the formula Ib by first reactingthe diamine of the formula VI with the difluorotriazine dye of theformula VIII to form a dye of the formula IX ##STR21## where R¹, R², R³,R⁴, R⁵, R⁶ and Y are each as defined above, and then reacting this dyewith the dye of the formula V.

Copper formazan reactive dyes of the formula Id ##STR22## where R¹, R²,R³, R⁴, R⁵, R⁶ and X¹ are each as defined above, are obtained forexample by reacting cyanuric chloride with dyes of the formula VIII orIX.

Copper formazan reactive dyes of the formula Ic are obtained for exampleby reacting an amine of the formula X ##STR23## where R⁹ and R¹⁰ areeach as defined above, with a dye of the formula Id or, alternatively,by reacting an amine of the formula X with cyanuric fluoride to forminitially a difluorotriazine of the formula XI ##STR24## where R⁹ andR¹⁰ are each as defined above, which is then subjected to a furtherreaction with a dye of the formula VIII or IX.

Copper formazan reactive dyes of the formula Ie are obtained for exampleby reacting a dichlorotriazine dye of the formula Id with a copperformazan dye of the formula VII or IX. However, it is also possible toprepare the dye of the formula Ie according to the present invention byreaction of the monochlorotriazine dye of the formula VII or of themonofluorotriazine dye of the formula IX with cyanuric fluoride to forminitially a double attachment dye of the formula XII ##STR25## where R¹,R², R³, R⁴, X¹ and Z¹ are each as defined above, and further reaction ofthe double attachment dye of the formula XII with a dye of the formulaVII or IX.

A further possible way of synthesizing dyes of the formula Ie consistsin reacting a diamine of the formula VI with a dye of the formula Id orXII to form a dye of the formula XIV ##STR26## where R¹, R², R³, R⁴, Z¹,Z², X¹ and X² are each as defined above, and further reacting theproduct with a dichlorotriazine dye of the formula V or adifluorotriazine dye of the formula VIII.

The copper formazan dye parent to the radical of the formula II (in theparent, the --NH-- group in the formula II is saturated by hydrogen) canlikewise be prepared in a conventional manner. It is obtained forexample by coupling the diazonium salt of1-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid with aphenylhydrazone of the formula XV ##STR27## where R¹, R², R³ and R⁴ areeach as defined above, then complexing the reaction product with copperby reaction with copper sulfate or copper chloride, and finallyconverting the acetylamino group into the free amino group by hydrolysis(cf. Houben-Weyl, Methoden der Organischen Chemie, Volume 10/2, pages487 and 480, 1967).

Further preparation details may be found in the Examples.

The novel copper formazan reactive dyes of the formual I are suitablefor dyeing and printing hydroxyl- or nitrogen-containing organicsubstrates. Such substrates are for example leather and fiber materialwhich predominantly contains natural or synthetic polyamides or naturalor regenerated cellulose. The novel dyes are preferably suitable fordyeing and printing textile material based on cotton. They areparticularly advantageously applied to cotton by the exhaust method.

The dyes according to the present invention produce dyeings in mediumblue shades. They are readily soluble and have a very high fastnesslevel, in particular wet fastness. The color buildup in medium to deepdyeings is particularly high.

The following Examples will illustrate the invention in more detail:

EXAMPLE 1

19.5 g of cyanuric chloride were added to a solution of 62 g of thesodium salt of the compound of the formula ##STR28## in 150 ml of waterand 150 g of ice. The pH of the reaction mixture was maintained at 5-5.5with sodium bicarbonate until the acylation had ended. After 2 hours, 19g of 4-amino-2-(N-methylamino)benzenesulfonic acid, dissolved in 200 mlof water, were added. The suspension was heated to 40° C., and the pHwas maintained at 7-8 by the addition of sodium bicarbonate.

After 6 hours, the resulting dye of the formula ##STR29## was admixed insolution with 78 g of the dichlorotriazine dye of the formula ##STR30##formed, as described above, by reaction of 62 g of the sodium salt ofthe compound of the formula ##STR31## with 19.5 g of cyanuric chloride.The suspension was heated to 60° C., and the pH was maintained at 7-7.5by the addition of sodium bicarbonate. After 6 hours, the resulting dyeof the formula ##STR32## was salted out with sodium chloride in the formof its sodium salt, filtered off and dried. The dark blue powderobtained is very readily water-soluble and dyes cotton in bright blueshades. The dyeings are light- and wet-fast. They show remarkablestability to oxidative influences.

The method of Example 1 was used to obtain the dyes indicated in Table1, which dye cotton in fast brilliant medium blue shades. ##STR33##

                                      TABLE 1                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                           L.sup.2                                                                           L.sup.3                                                                           L.sup.4                                                                           L.sup.5                                                                          L.sup.6                                                                           L.sup.7                                                                           L.sup.8                                                                           L.sup.9                                                                           L.sup.10                                                                          L.sup.11                            __________________________________________________________________________    2  H   H   H   SO.sub.3 H                                                                        Et H   H   H   H   SO.sub.3 H                                                                        H                                   3  H   H   SO.sub.3 H                                                                        H   Me H   H   H   H   H   SO.sub.3 H                          4  H   H   SO.sub.3 H                                                                        H   Et H   H   H   H   H   SO.sub.3 H                          5  H   H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          6  H   H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   7  SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   H   SO.sub.3 H                                                                        H                                   8  SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   H   H   SO.sub.3 H                          9  SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          10 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   H                                   11 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   SO.sub.3 H                                                                        H   H                                   12 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   SO.sub.3 H                                                                        H   H   H   H                                   13 H   SO.sub.3 H                                                                        H   H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          14 SO.sub.3 H                                                                        H   H   H   Me SO.sub.3 H                                                                        H   H   H   H   H                                   15 H   H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   16 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   H   H   SO.sub.3 H                                                                        H                                   17 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   18 H   H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          19 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   H   H   H   H                                   __________________________________________________________________________

EXAMPLE 20

14 g of trifluorotriazine were added dropwise into a solution of 62 g ofthe sodium salt of the compound of the formula ##STR34## in 150 ml ofwater and 150 g of ice at 0° C. in the course of 30 minutes, and the pHwas maintained between 4.9 and 5.2. After 30 minutes, 95.5 g of thesodium salt of the dye of the formula ##STR35## obtained similarly tothe method described in Example 1, were added, and pH 6.5-7 wasmaintained at 15° C. for 6 hours by the addition of sodium bicarbonate.Thereafter the resulting dye of the formula ##STR36## was salted outwith sodium chloride in the form of its sodium salt, filtered off anddried. The dark blue dye powder obtained is very readily water-solubleand dyes cotton in bright blue shades. The dyeings are light- andwet-fast. They show remarkable stability to oxidative influences.

The method of Example 20 was used to obtain the dyes indicated in Table2, which dye cotton in fast brilliant medium blue shades.

                                      TABLE 2                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                           L.sup.2                                                                           L.sup.3                                                                           L.sup.4                                                                           L.sup.5                                                                          L.sup.6                                                                           L.sup.7                                                                           L.sup.8                                                                           L.sup.9                                                                           L.sup.10                                                                          L.sup.11                            __________________________________________________________________________    21 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        H                                   22 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   SO.sub.3 H                          23 H   H   SO.sub.3 H                                                                        H   Me H   H   H   SO.sub.3 H                                                                        H   H                                   24 H   H   SO.sub.3 H                                                                        H   Et H   H   H   SO.sub.3 H                                                                        H   H                                   25 H   H   H   SO.sub.3 H                                                                        Et H   H   H   H   SO.sub.3 H                              26 H   H   H   SO.sub.3 H                                                                        Et H   H   H   H   SO.sub.3 H                                                                        H                                   27 H   H   SO.sub.3 H                                                                        H   Me H   H   H   H   H   SO.sub.3 H                          28 H   H   SO.sub.3 H                                                                        H   Et H   H   H   H   H   SO.sub.3 H                          29 H   H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          30 H   H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   31 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   H   SO.sub.3 H                                                                        H                                   32 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   H   H   SO.sub.3 H                          33 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          34 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   SO.sub.3 H                                                                        H   H   H                                   35 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   H   H   SO.sub.3 H                                                                        H   H                                   36 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   Me H   SO.sub.3 H                                                                        H   H   H   H                                   37 H   SO.sub.3 H                                                                        H   H   Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          38 SO.sub.3 H                                                                        H   H   H   Me SO.sub.3 H                                                                        H   H   H   H   H                                   39 H   H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   40 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   H   H   SO.sub.3 H                                                                        H                                   41 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   42 H   H   H   SO.sub.3 H                                                                        Me H   H   SO.sub.3 H                                                                        H   H   SO.sub.3 H                          43 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H   H   H   H   H   H                                   __________________________________________________________________________

EXAMPLE 44

19.5 g of cyanuric chloride were added to a solution of 95.5 g of thesodium salt of the dye of the formula ##STR37## obtained as described inExample 1, in 150 ml of water and 150 g of ice at 0° C. The pH of thereaction mixture was maintained at 5-5.5 with sodium bicarbonate untilthe acylation had ended. After 3 hours at 5° C. the resulting dye of theformula ##STR38## was filtered off and dried. The dark blue dye powderobtained is very readily water-soluble and dyes cotton in bright blueshades. The dyeings are light- and wet-fast. They show remarkablestability to oxidative influences.

The method of Example 44 was used to obtain the dyes indicated in Table3, which dye cotton in fast brilliant medium blue shades. ##STR39##

                  TABLE 3                                                         ______________________________________                                        Ex.                                                                           No.   L.sup.1 L.sup.2  L.sup.3                                                                              L.sup.4                                                                              L.sup.5                                                                            L.sup.6                             ______________________________________                                        45    H       H        H      SO.sub.3 H                                                                           Et   H                                   46    H       H        SO.sub.3 H                                                                           H      Me   H                                   47    H       H        SO.sub.3 H                                                                           H      Et   H                                   48    SO.sub.3 H                                                                            H        SO.sub.3 H                                                                           H      Me   H                                   49    SO.sub.3 H                                                                            H        H      SO.sub.3 H                                                                           Me   H                                   50    H       SO.sub.3 H                                                                             H      SO.sub.3 H                                                                           Me   H                                   51    SO.sub.3 H                                                                            H        H      H      Me   H                                   52    SO.sub.3 H                                                                            H        H      H      Me   SO.sub.3 H                          ______________________________________                                    

EXAMPLE 53

18 g of 3-aminobenzenesulfonic acid were added at 20° C. to a solutionof 111.5 g of the sodium salt of the dye of the formula ##STR40##obtained as described in Example 44, in 300 ml of water, and the mixturewas stirred at 40° C. for 3 hours, during which pH 6.5-7.5 wasmaintained by the addition of sodium bicarbonate. Thereafter theresulting dye of the formula ##STR41## was salted out with sodiumchloride in the form of its sodium salt, filtered off and dried. Thedark blue dye powder obtained is very readily water-soluble and dyescotton in bright blue shades. The dyeings are light- and wet-fast. Theyshow remarkable stability to oxidative influences.

The method of Example 53 was used to obtain the dyes indicated in Table4, which dye cotton in fast brilliant medium blue shades. ##STR42##

                                      TABLE 4                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                           L.sup.2                                                                           L.sup.3                                                                           L.sup.4                                                                           L.sup.5                                                                          L.sup.6                                                                          L.sup.7   L.sup.8                                    __________________________________________________________________________    54 H   H   H   SO.sub.3 H                                                                        Et H                                                                                          H                                          55 H   H   H   SO.sub.3 H                                                                        Me H                                                                                 ##STR43##                                                                              H                                          56 H   H   H   SO.sub.3 H                                                                        Me H                                                                                 ##STR44##                                                                              H                                          57 H   H   SO.sub.3 H                                                                        H   Me H                                                                                 ##STR45##                                                                              H                                          58 H   H   H   SO.sub.3 H                                                                        Me H  H         H                                          59 H   H   H   SO.sub.3 H                                                                        Et H  H         H                                          60 H   H   H   SO.sub.3 H                                                                        Me Me                                                                                ##STR46##                                                                              H                                          61 H   H   H   SO.sub.3 H                                                                        Et Me                                                                                ##STR47##                                                                              H                                          62 H   H   H   SO.sub.3 H                                                                        Me Et                                                                                ##STR48##                                                                              H                                          63 H   H   SO.sub.3 H                                                                        H   Me Me                                                                                ##STR49##                                                                              H                                          64 H   H   SO.sub.3 H                                                                        H   Me H  H         H                                          65 H   H   SO.sub.3 H                                                                        H   Me Et H         H                                          66 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        Et H  H         Me                                         67 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H  H         H                                          68 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        Me H  H         H                                          69 SO.sub.3 H                                                                        H   H   H   Me H  H         SO.sub.3 H                                 70 H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        Me H  H         H                                          __________________________________________________________________________

EXAMPLE 71

95.5 g of the sodium salt of the dye of the formula ##STR50## obtainedas described in Example 1, were added to a solution of 111.5 g of thesodium salt of the dye of the formula ##STR51## obtained as described inExample 44, in 1000 ml of water, and at 60° C. the suspension wasmaintained at pH 6.5-7.0 by the addition of sodium bicarbonate. After 6hours the resulting dye of the formula ##STR52## was salted out withsodium chloride in the form of its sodium salt, filtered off and dried.The dark blue dye powder obtained is very readily water-soluble and dyescotton in bright blue shades. The dyeings are light- and wet-fast. Theyshow remarkable stability to oxidative influences.

The method of Example 71 was used to obtain the dyes indicated in Table5 which dye cotton in fast brilliant medium blue shades. ##STR53##

                                      TABLE 5                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                            L.sup.2                                                                           L.sup.3                                                                            L.sup.4                                                                           L.sup.5                                                                           L.sup.6                                                                           L.sup.7                                                                           L.sup.8                                      __________________________________________________________________________    72 H    SO.sub.3 H                                                                        H    H   Me  SO.sub.3 H                                                                        H   Me                                           73 H    SO.sub.3 H                                                                        H    H   Me  H   SO.sub.3 H                                                                        Me                                           74 H    SO.sub.3 H                                                                        H    H   Me  SO.sub.3 H                                                                        H   Et                                           75 H    SO.sub.3 H                                                                        H    H   Me  H   SO.sub.3 H                                                                        Et                                           76 H    H   SO.sub.3 H                                                                         H   Me  SO.sub.3 H                                                                        H   Et                                           77 H    H   SO.sub.3 H                                                                         H   Me  H   SO.sub.3 H                                                                        Et                                           78 H    H   SO.sub.3 H                                                                         H   Et  H   SO.sub.3 H                                                                        Et                                           79 SO.sub.3 H                                                                         H   SO.sub.3 H                                                                         H   Me  H   SO.sub.3 H                                                                        Me                                           80 SO.sub.3 H                                                                         SO.sub.3 H                                                                        H    H   Me  SO.sub.3 H                                                                        H   Me                                           81 SO.sub.3 H                                                                         SO.sub.3 H                                                                        H    SO.sub.3 H                                                                        Me  SO.sub.3 H                                                                        H   Me                                           __________________________________________________________________________

EXAMPLE 82

14 g of trifluorotriazine were added dropwise to a solution of 70 g ofthe sodium salt of the compound of the formula ##STR54## in 150 ml ofwater and 150 g of ice at 0° C. in the course of 30 minutes, and pH4.9-5.2 was maintained. After 30 minutes, 20 g of3-(N-methylamino)-4-hydroxysulfonylaniline were added, and pH 6.5-7.0was maintained with sodium bicarbonate. After 30 minutes, 78 g of thedichlorotriazine dye of the formula ##STR55## obtained as described inExample 1, were added, and pH 7-7.5 was maintained with sodiumbicarbonate. After 6 hours, the resulting dye of the formula ##STR56##was salted out with sodium chloride in the form of its sodium salt,filtered off and dried. The dark blue dye powder obtained is veryreadily water-soluble and dyes cotton in bright blue shades. The dyeingsare light- and wet-fast. They show remarkable stability to oxidativeinfluences.

The method of Example 82 was used to obtain the dyes indicated in Table6, which dye cotton in fast brilliant medium blue shades. ##STR57##

                                      TABLE 6                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                           L.sup.2                                                                           L.sup.3                                                                           L.sup.4                                                                           L.sup.5                                                                          L.sup.6                                                                           L.sup.7                                                                           L.sup.8                                                                           L.sup.9                                                                           L.sup.10                                                                          L.sup.11                            __________________________________________________________________________    83 H   H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          84 H   H   H   SO.sub.3 H                                                                        C.sub.2 H.sub.5                                                                  H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          85 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   86 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        H   H   H                                   87 H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        H   H   H                                   88 H   H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        SO.sub.3 H                          89 H   H   SO.sub.3 H                                                                        H   C.sub.2 H.sub.5                                                                  H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          90 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   CH.sub.3                                                                         SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   H   H                                   __________________________________________________________________________

19 g of trichlorotriazine were added to a solution of 10 g of the sodiumsalt of the compound of the formula ##STR58## in 150 g of water and 150g of ice at 0° C. in the course of 30 minutes, and pH 4.9-5.2 wasmaintained. After 30 minutes, 95.5 g of the sodium salt of the dye ofthe formula ##STR59## obtained by the method described in Example 1,were added, and pH 6.5-7 was maintained at 15° C. for 6 hours by theaddition of NaHCO₃. Thereafter the resulting dye of the formula##STR60## was salted out with sodium chloride in the form of its sodiumsalt, filtered off and dried. The dark blue dye powder obtained is veryreadily water-soluble and dyes cotton in bright blue shades. The dyeingsare light- and wet-fast. They show remarkable stability to oxidativeinfluences.

The method of Example 91 was used to obtain the dyes indicated in Table7, which dye cotton in fast brilliant medium blue shades. ##STR61##

                                      TABLE 7                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              L.sup.1                                                                           L.sup.2                                                                           L.sup.3                                                                           L.sup.4                                                                           L.sup.5                                                                          L.sup.6                                                                           L.sup.7                                                                           L.sup.8                                                                           L.sup.9                                                                           L.sup.10                                                                          L.sup.11                            __________________________________________________________________________    92 H   H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          93 H   H   H   SO.sub.3 H                                                                        C.sub.2 H.sub.5                                                                  H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          94 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H                                   95 SO.sub.3 H                                                                        H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        H   H   H                                   96 H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        H   H   H                                   97 H   H   H   SO.sub.3 H                                                                        CH.sub.3                                                                         H   H   H   SO.sub.3 H                                                                        SO.sub.3 H                                                                        SO.sub.3 H                          98 H   H   SO.sub.3 H                                                                        H   C.sub.2 H.sub.5                                                                  H   H   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        SO.sub.3 H                          99 SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   CH.sub.3                                                                         SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        H   H   H                                   __________________________________________________________________________

We claim:
 1. A copper formazan reactive dye of the formula (I):##STR62## in the form of the free acid or in the form of a salt thereof,wherein n is 0 or 1,X¹ and X³ are each chlorine, X² is chlorine, and Ais a radical of the formula (IIa): ##STR63## wherein R¹ is hydrogen,hydroxysulfonyl, C₁ -C₄ -alkoxy or chlorine, R² is hydrogen orhydroxysulfonyl, and one of the two radicals R³ and R⁴ is hydrogen andthe other is hydroxysulfonyl, or when at least one of the two radicalsR¹ and R² is hydroxysulfonyl, R³ and R⁴ are each simultaneously hydrogenor a radical of the formula (IIb): ##STR64## wherein R¹ and R² are eachas defined above, Z¹ and Z² are identical or different, each beingindependently of the other a radical of the formula (III): ##STR65##wherein R⁵ and R⁶ are identical or different, each being independentlyof the other hydrogen or unsubstituted or cyano- or hydroxyl-substitutedC₁ -C₄ -alkyl, Y is hydroxyl or a radical of the formula NR⁷ R⁸, whereinR⁷ and R⁸ are identical or different, each being independently of theother hydrogen or unsubstituted or cyano-, hydroxyl- orhydroxysulfonyl-substituted C₁ -C₄ -alkyl, where the radicals R⁷ and R⁸together with a nitrogen atom joining them form a heterocyclic ringselected from the group consisting of pyrrolidino, piperidino,morpholino, piperazino and N-(C₁ -C₄ -alkyl)piperazino, and B is aradical NR⁹ R¹⁰, wherein R⁹ and R¹⁰ are identical or different, eachbeing independently of the other hydrogen or unsubstituted or cyano-,hydroxyl-, or hydroxysulfonyl-substituted C₁ -C₄ -alkyl, or one of thetwo radicals R⁹ and R¹⁰ are phenyl which is unsubstituted or substitutedby hydroxysulfonyl, sulfamoyl, C₁ -C₄ -alkyl, halogen, cyano or C₁ -C₄-alkoxy, or B is as defined for the above-mentioned radical A, with theproviso that: a) R⁵ and R⁶ are not both hydrogen, b) when n is 0 and Bis A, A and B are different, and c) when n is 1, B is A.
 2. The copperformazan reactive dye of claim 1, wherein Y and B are each selected fromthe group consisting of amino, mono- or dimethylamino, mono- ordiethylamino, mono- or dipropylamino, mono- or diisopropylamino, mono-or dibutylamino, N-methyl-N-ethylamino, mono- or bis(2-cyanoethyl)amino,mono- or bis(2-hydroxyethyl)amino, N-ethyl-N-(2-cyanoethyl)amino,N-ethyl-N-(2-hydroxyehtyl)amino, 2-hydroxysulfonylethylamino orN-ethyl-N-(2-hydroxysulfonylethyl)-amino.
 3. The copper formazanreactive dye of claim 1, wherein said salt is a lithium, sodium,potassium or ammonium salt.
 4. The copper formazan reactive dye of claim1, wherein Z¹ and Z² are each a radical of the formula (IIIa): ##STR66##wherein R⁵ and R⁶ are each independently of the other hydrogen, methylor ethyl.
 5. The copper formazan reactive dye of claim 1, wherein Z¹ andZ² are each a radical of the formula (IIIb): ##STR67## wherein R⁶ ismethyl or ethyl.
 6. The copper formazan reactive dye of claim 1, whichhas the formula (Ib): ##STR68## wherein R⁶ is methyl or ethyl.
 7. Thecopper formazan reactive dye of claim 1, which has the formula (Ic):##STR69## wherein Z¹ is a radical of the formula (IIIb): ##STR70##wherein R⁶ is methyl or ethyl.
 8. The copper formazan reactive dye ofclaim 1, which has the formula (Id): ##STR71## wherein A is as definedabove, X¹ is chlorine and Z is a radical of the formula (IIIb):##STR72## wherein R⁶ is methyl or ethyl.
 9. A copper formazan reactivedye of the formula (Ie): ##STR73## wherein A is a radical of the formula(IIa): ##STR74## wherein R¹ is hydrogen, hydroxysulfonyl, C₁ -C₄ -alkoxyor chlorine,R² is hydrogen or hydroxysulfonyl, and one of the tworadicals R³ and R⁴ is hydrogen and the other is hydroxysulfonyl, or whenat least one of the two radicals R¹ and R² is hydroxysulfonyl, R³ and R⁴are each simultaneously hydrogen or a radical of the formula (IIb):##STR75## wherein R¹ and R² are each as defined above; X¹, X² and X³ areeach independently of the others chlorine or fluorine; and Z¹ and Z² areeach independently of the other a radical of the formula (IIIb):##STR76## wherein R⁶ is methyl or ethyl.